CN109095923A - A kind of preparation method and luminescent ceramic composite of luminescent ceramic composite - Google Patents
A kind of preparation method and luminescent ceramic composite of luminescent ceramic composite Download PDFInfo
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- CN109095923A CN109095923A CN201710470370.5A CN201710470370A CN109095923A CN 109095923 A CN109095923 A CN 109095923A CN 201710470370 A CN201710470370 A CN 201710470370A CN 109095923 A CN109095923 A CN 109095923A
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- sintering aid
- ceramic composite
- luminescent ceramic
- preparation
- fluorescent powder
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- 239000000919 ceramic Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 142
- 239000000843 powder Substances 0.000 claims abstract description 96
- 239000000463 material Substances 0.000 claims abstract description 70
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 230000008595 infiltration Effects 0.000 claims abstract description 21
- 238000001764 infiltration Methods 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 7
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 abstract description 16
- 239000007791 liquid phase Substances 0.000 abstract description 7
- 238000001802 infusion Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 55
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 30
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 25
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 22
- 239000000395 magnesium oxide Substances 0.000 description 18
- 239000000725 suspension Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000012752 auxiliary agent Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 150000004703 alkoxides Chemical class 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000002223 garnet Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910017970 MgO-SiO2 Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VGMFHMLQOYWYHN-UHFFFAOYSA-N Compactin Natural products OCC1OC(OC2C(O)C(O)C(CO)OC2Oc3cc(O)c4C(=O)C(=COc4c3)c5ccc(O)c(O)c5)C(O)C(O)C1O VGMFHMLQOYWYHN-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- AJLFOPYRIVGYMJ-UHFFFAOYSA-N SJ000287055 Natural products C12C(OC(=O)C(C)CC)CCC=C2C=CC(C)C1CCC1CC(O)CC(=O)O1 AJLFOPYRIVGYMJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- ORPJQHHQRCLVIC-UHFFFAOYSA-N magnesium;propan-2-olate Chemical compound CC(C)O[Mg]OC(C)C ORPJQHHQRCLVIC-UHFFFAOYSA-N 0.000 description 1
- AJLFOPYRIVGYMJ-INTXDZFKSA-N mevastatin Chemical compound C([C@H]1[C@@H](C)C=CC2=CCC[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)C[C@@H]1C[C@@H](O)CC(=O)O1 AJLFOPYRIVGYMJ-INTXDZFKSA-N 0.000 description 1
- BOZILQFLQYBIIY-UHFFFAOYSA-N mevastatin hydroxy acid Natural products C1=CC(C)C(CCC(O)CC(O)CC(O)=O)C2C(OC(=O)C(C)CC)CCC=C21 BOZILQFLQYBIIY-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
- C04B35/505—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3229—Cerium oxides or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
Abstract
The present invention relates to a kind of preparation method of luminescent ceramic composite and luminescent ceramic composites.The preparation method of luminescent ceramic composite of the invention is the following steps are included: the green compact comprising fluorescent powder and the encapsulating material and optional sintering aid a that are used to encapsulate fluorescent powder are infiltrated in the precursor solution of sintering aid b, and the green compact by infiltration are calcined so that the precursor of sintering aid b is changed into infiltration-calcining step of sintering aid b；Green compact after calcining are sintered, to obtain the sintering step of luminescent ceramic composite.The present invention improves the addition manner of sintering aid by liquid phase infusion method, to obtain, relative density is higher and the luminescent ceramic composite of excellent in optical properties.
Description
Technical field
The present invention relates to a kind of preparation methods of luminescent ceramic composite, and the luminous pottery prepared by the method
Porcelain composite material.
Background technique
The laser fluorescence technology of blue laser excitation fluorescent material acquisition visible light, the light source technology completely new as one kind,
It being developed rapidly in laser display field, each enterprise has fallen over each other to release the laser light source for the various power for meeting different markets,
And achieve huge success.The hot and difficult issue of current research is developed newly primarily directed to the characteristic of LASER Excited Fluorescence powder
The fluorescent material (wavelength conversion material, luminescent material) of type, wherein these materials must possess outstanding performance, such as optical transition
High-efficient, brightness is high, and unit light-emitting area is able to bear more high power laser illumination, has high thermal conductivity, service life length etc..Stone
Garnet is most common laser-based because of its thermal conductivity, high mechanical strength and good chemical stability with higher
Material, including yttrium-aluminium-garnet (Y3Al5O12, YAG), Luetcium aluminum garnet (Lu3Al5O12, LuAG), yttrium gallium garnet
(Y3Ga5O12, YGG), Gd-Ga garnet (Gd3Ga5O12, GGG), lutetium Ga garnet (Lu3Ga5O12, LuGG) etc..
Luminescent ceramic since it is with preferable heat resistance and excellent thermal conductivity, be at present ideal luminescent material it
One.But traditional YAG pure phase luminescent ceramic is also weaker than silica gel and glass-encapsulated Combined illuminator on luminescent properties；It is special
When being not Ultrathin packaging, the loss of light efficiency caused by interface is totally reflected is very big.Therefore, fluorescent powder is packaged using ceramic material
It is the direction for being worth further investigation.YAG material package YAG such as undoped YAG phase pure material or difference Ce doping is glimmering
Light powder prepares YAG-YAG:Ce fluorescent powder or Ce:YAG-YAG:Ce phosphor ceramic material, can obtain and shine than pure phase YAG
The more excellent optical property of ceramics.
Current phosphor ceramic material, generally requires by the way of hot pressed sintering or other high-pressure sinter modes,
High performance ceramic body can be obtained.But hot pressed sintering the device is complicated, production environment require stringent, mold materials require it is high,
Energy consumption is big, production efficiency is lower, higher cost.
In addition, about the addition of sintering aid, common method is all that will make pottery in the preparation of luminescent ceramic composite
Porcelain powder and sintering aid mix as homogeneously as possible, be further filled in mold carry out it is pre-stamped.Patent document 1
(CN1837142A) a kind of preparation method of Luetcium aluminum garnet-base transparent ceramic, the Luetcium aluminum garnet-base transparent ceramic are disclosed
By the L μ that will be used as raw material2O3、RE2O3、Al2O3Equal oxide powders or the L μ as raw material3-xRExAl5O12With as sintering
The SiO of auxiliary agent2Or ethyl orthosilicate (TEOS) mixing, then using in the moulding process such as dry-pressing formed, cold isostatic compaction
Any one is formed, and is carried out the processing such as pressureless sintering or hot pressed sintering, annealing later and is obtained.
In addition, patent document 2 (CN104177092A) discloses a kind of method for preparing transparent luminescent ceramic, the method
It helping using the compound that general structure is RX (wherein R indicates that light emitting ionic, X indicate volatile anion) while as sintering
The constitutive material of agent and activation ion, and the RX compound is mixed with raw material, it then ground, suppressed, is sintered and (being burnt
Knot vacuum-sintering, atmosphere sintering, hot pressed sintering can be used), annealing etc. processing.In above patent document 1 and 2 by raw material powder with
In the case that sintering aid directly mixes, the problem of due to powder flowbility and fillibility, will lead to will form between particles
Gap.The presence in gap will affect the performance of material.
That therefore, it is necessary to a kind of gaps is less, relative density is higher and more excellent performance of luminescent ceramic composite with
And the preparation method of this material.
Summary of the invention
Problems to be solved by the invention
In the preparation of current luminescent ceramic, ceramic sintering densification process, mainly by ceramic body in sintering process
Inside forms liquid phase to push.In normal pressure or vacuum-sintering, material powder can be blended in advance, and it is preparatory to reuse mold
Green compact are pressed into, sintering in furnace is then placed in.About the addition of sintering aid, as described above, common method, being all will be ceramic
Powder and sintering aid mix as homogeneously as possible, be further filled in mold carry out it is pre-stamped.But due to powder flowbility
And the problem of fillibility, for powder during inserting mold and stress is pressed molding, the degree of piling up of powder is variant
's；And ideal green compact, the pattern at each position all should be relatively uniform.With prepare YAG-YAG:Ce fluorescent powder or
It is illustrated in case where MgO is as sintering aid when Ce:YAG-YAG:Ce fluorescent powder.Ideal situation as shown in Figure 1,
Around YAG:Ce fluorescent powder grain, MgO is evenly distributed between them YAG or YAG:Ce phase distribution of particles.But
In actual green compact, structure as shown in Figure 2 can more occur in internal structure；The shifting this is because powder is pressurized in a mold
When dynamic, be under pressure the influence that inconsistent, intergranular friction power is uneven and mobility of particle is inconsistent, will form between particle
Such as the gap in Fig. 2.Due to the presence in these gaps, common green compact can not be by abundant during normal pressure or vacuum-sintering
Substance shift to fill gap, gap finally will become the hole of closed stomata or connection, influence the performance of material.
The solution to the problem
To solve the above problems, the present invention provides a kind of preparation method of luminescent ceramic composite, which is characterized in that institute
State method the following steps are included:
Green compact comprising fluorescent powder and the encapsulating material and optional sintering aid a that are used to encapsulate fluorescent powder are infiltrated on
In the precursor solution of sintering aid b, and the green compact by infiltration are calcined so that the precursor of sintering aid b is changed into sintering aid
Infiltration-calcining step of b；
Green compact after calcining are subjected to normal pressure-sintered or vacuum-sintering, to obtain the sintering of luminescent ceramic composite
Step.
The preparation method of luminescent ceramic composite according to the present invention, wherein the total amount of sintering aid is fluorescent powder
With the 0.1~5% of encapsulating material gross mass, preferably 0.5%~1.5%.
The preparation method of luminescent ceramic composite according to the present invention, the wherein precursor solution of sintering aid b
Concentration is 0.01~10M, preferably 0.1M~10M, more preferable 0.1~1M.
The preparation method of luminescent ceramic composite according to the present invention, wherein the green compact immerse the leaching of sintering aid
The profit time be 10min~120min, preferably 30min~90min, more preferable 40min~60min, and/or, calcination temperature 200
~500 DEG C, preferably 300~500 DEG C, more preferable 350~450 DEG C.
The preparation method of luminescent ceramic composite according to the present invention, wherein above infiltration-calcining step can weigh
It carries out 1~5 time, preferably 1~3 time again.
The preparation method of luminescent ceramic composite according to the present invention further comprises the preparation step of green compact
Suddenly, which includes by the mixing comprising fluorescent powder and the encapsulating material and optional sintering aid a that are used to encapsulate fluorescent powder
Powder carries out ball milling, drying, sieving, compacting, to obtain green compact.
The preparation method of luminescent ceramic composite according to the present invention, wherein sintering aid a and b independently are
MgO、SiO2、CaF2、BaF2One or more of.
The preparation method of luminescent ceramic composite according to the present invention, wherein the precursor of sintering aid b is sintering
The inorganic salts or alkoxide of auxiliary agent.
The present invention also provides a kind of luminescent ceramic composites, which is characterized in that it includes fluorescent powder, described for encapsulating
The encapsulating material and sintering aid of fluorescent powder.
Wherein, the relative density of the luminescent ceramic composite is 94% or more.
Wherein, the particle of the encapsulating material is uniformly distributed in around the particle of the fluorescent powder, the sintering aid point
It is distributed in the crystal boundary of the encapsulating material.
Wherein, in luminescent ceramic composite the total amount of sintering aid be fluorescent powder and encapsulating material gross mass 0.1~
5%, preferably 0.5%~1.5%.Wherein, the total amount of sintering aid is sintering aid a and b quality sum.
Wherein, sintering aid a and b independently are MgO, SiO2、CaF2、BaF2One or more of.
Wherein, encapsulating material YAG, YAG:Ce or Al2O3One or more of.
The effect of invention
In the preparation method of luminescent ceramic composite of the invention, sintering is immersed by the green compact for making precompressed and is helped
In the precursor solution of agent, so that the gap inside green compact is sintered the precursor solution filling of auxiliary agent, then take the green compact after infiltration
It dries, calcine out, promote the sintering aid content in green compact internal voids, according to actual requirement, green compact can repeatedly soak
Profit, to obtain the auxiliary agent content for meeting demand.Green compact after infiltration-calcining auxiliary agent technique, the structure meeting of internal such as Fig. 2
Become the structure such as Fig. 3；By Fig. 2 and Fig. 3 as it can be seen that the content of auxiliary agent (by taking MgO as an example) increases around gap, thus in normal pressure
Liquid phase in sintering or vacuum-sintering process void can be more significant, and the particle around gap can be promoted to carry out substance transfer,
Be conducive to eliminate stomata, the relative density after improving green sintering.Therefore, the present invention is not needed using the device is complicated, production ring
Border requirement is stringent, mold materials require height, energy consumption is big, production efficiency is lower, the hot pressed sintering mode of high production cost, leads to
It crosses using green body liquid phase infusion method, improves the addition manner of sintering aid, made under the conditions of normal pressure-sintered or vacuum-sintering
Obtained the luminescent ceramic composite that gap is less, relative density is higher and optical property is more excellent.
Detailed description of the invention
Fig. 1 is green compact inner part cloth uniformly each phase powder particle schematic diagram.
Fig. 2 is the non-uniform each phase powder particle schematic diagram of green compact inner part cloth.
Fig. 3 is each phase powder particle distribution schematic diagram in green compact inside after infiltration-calcining.
Fig. 4 is the launching light spectrogram of the sample prepared in the sample and comparative example 1 prepared in embodiment 1.
Fig. 5 is a kind of preparation step of embodiment of luminescent ceramic composite.
Fig. 6 is the preparation step of the another embodiment of luminescent ceramic composite.
Specific embodiment
The preparation method of luminescent ceramic composite of the present invention is explained in more detail below by way of specific embodiment
Specific steps.
As shown in figure 5, the preparation method of luminescent ceramic composite of the invention includes the following steps:
S:1, the preparation step of green compact；
S:2, infiltration-calcining step；
S:4, sintering step.
In some other embodiment, as shown in fig. 6, being further comprised the steps of: before step S:4
S:3: tableting step.
Being described as follows for above step is described.
S:1,The preparation step of green compactIn the present invention, green compact will be by that will include fluorescent powder, the encapsulation for being used to encapsulate fluorescent powder
The mixed-powder of material and optional sintering aid a carry out the step of ball milling, drying, sieving, compacting and are made.
Specifically, by the mixing comprising fluorescent powder, the encapsulating material and optional sintering aid a that are used to encapsulate fluorescent powder
Powder is fitted into polytetrafluoroethylene (PTFE) ball grinder, is added suitable ethyl alcohol as abrasive solvents, is not used any dispersing agent, with super
The zirconia ball of low mill mistake rate carries out ball milling.Ball-milling Time can select as needed, therefore be not particularly limited, but usually 1~
120min, preferably 30~50min.If Ball-milling Time is too long, it is easily damaged the grain morphology of fluorescent powder, influences to shine
Performance.
After ball milling, then dry to obtain dry powder.It is preferred that dry using vacuum constant temperature, drying temperature can for 40~
120 DEG C, preferably 50~100 DEG C, drying time can be 1h~12h, preferably 4~8h.Later, 80 mesh, 150 mesh, 200 meshes are crossed,
Obtain the raw material powder of high fluidity.
Then, the raw material powder of acquisition is suppressed, is then demoulded, to obtain green compact.The method of compacting is not special
It limits, conventional drawing method such as cold isostatic pressing process etc. can be used to carry out.The pressure of compacting usually in 5~200MPa, preferably 15
Under~100MPa pressure.It if pressure is too small, will lead to that hole is more larger, influence final sintering finished consistency.
Encapsulating material (hereinafter referred to as " encapsulating material ") when only including fluorescent powder in green compact and for encapsulating fluorescent powder
When, two kinds of powder are mixed.Also, the weight ratio of fluorescent powder and encapsulating material is 1:0.1~0.1:1, preferably 1:1.
It, usually will preparatory encapsulating material obtained and burning when in green compact including fluorescent powder, encapsulating material and sintering aid a
The mixed-powder of knot auxiliary agent a is mixed with fluorescent powder.Also, sintering aid a and the total mass ratio of fluorescent powder and encapsulating material are
(0.01~5): 100, preferably (0.05~1): 100.
Fluorescent powder is not particularly limited, and can be the commercial fluorescent powder of any resistance to 1300 degree or more high temperature.It is usually workable
The example of fluorescent powder includes YAG:RE, LuAG:RE, YGG:RE, GGG:RE and LuGG:RE, wherein RE be selected from Ce, Pr, Eu,
Element in Nd, Sm, Gd, Yb, Ho, Tm, Dy and Er.The mixed-powder of encapsulating material and sintering aid a are by by encapsulating material
Suspension mixed with the solution (hereinafter referred to as " solution a ") of the precursor of sintering aid a, precipitating reagent then is added so that they are total
Precipitating, is centrifuged later, washs, dries, calcines and cools down and obtain.Alternatively, can also by by encapsulating material with
The direct mixing and ball milling of sintering aid a is made.
The preparation method of suspension about encapsulating material is not particularly limited, as long as can be dispersed.For example, can
Using following methods: preparing the PEG aqueous solution of 1~3 mass %；50 grams of encapsulating material and 500 milliliters of PEG aqueous solutions are mixed
It closes；Then spare after 1~3h of ultrasound.Ultrasound is to make powder in the solution as far as possible to destroy the secondary agglomeration between particle
Ground dispersion.
The preparation method of the solution ie in solution a of the precursor of sintering aid a further explained below.The precursor of sintering aid a
It can be the water-soluble inorganic salt or alkoxide of sintering aid.When the precursor of sintering aid a is water-soluble metal inorganic salts, so as to burn
The weight ratio of the precursor and encapsulating material of tying auxiliary agent a is that required ratio weighs the precursor of appropriate sintering aid a and is configured to fit
The aqueous solution of the metal inorganic salt of suitable concentration.
After the completion of the suspension and solution a of material to be packaged are prepared, the two is preferably mixed with the volume ratio of 5:1, is obtained
Mixing suspension is placed on magnetic stirring apparatus and is stirred continuously, temperature setting be 20~80 DEG C, preferably 40~60 DEG C, revolving speed
For 100~300r/m, preferably 170~250r/m.Using ammonium hydrogen carbonate as precipitating reagent, it is made into the water-soluble of about 0.01~0.1mol/L
Liquid is slowly dropped into the mixing suspension being stirred continuously, and controls 8~10 or so, preferably until by suspension mixed pH value
It is 9~9.5.The pH value is kept, 1~5h of stirring, preferably 2~3h are continued, to obtain the composite granule suspension of co-precipitation.It closes
Suitable pH value is extremely important for the dispersion reconciliation flocculation of encapsulating material sub-micron-powder.Further, the present invention in YAG,
YAG:Ce or Al2O3At least one of can be used as encapsulating material according to actual needs.
Suspension is centrifugated, washing 2~8 times, preferably 3~5 times are carried out to the powder of acquisition, then 50~150
DEG C, preferably 50~100 DEG C be dried in vacuo 1~10 hour, preferably 1~5 hour.By the dry powder of acquisition 200~500 DEG C, preferably
It is calcined at 300~400 DEG C to remove impurity, keeps the temperature 1~5h, preferably 2~3h, it is air-cooled with furnace later, to obtain encapsulating material
With the mixed-powder of sintering aid a.
When the precursor of sintering aid a is alkoxide, using the method that alkoxide can be made to become colloidal sol.For example, can be used with
Lower preparation method: so that the mass ratio of the precursor of sintering aid a and encapsulating material is that required ratio weighs appropriate sintering aid a
Precursor, and prepare needed for concentration sintering aid a precursor ethanol solution；Into the ethanol solution, ammonium hydroxide is slowly added dropwise
(i.e. the mixed solution of ammonium hydroxide and deionized water, wherein the molar ratio of water and alkoxide is n to solutionWater/nAlkoxide=(3~4)/1), it adjusts
PH value is 9.0~9.5, and by the ageing of 12h, sol solution is made.It should be noted that wherein the ratio of water and alkoxide should
With alkoxide at least can partial hydrolysis be advisable, so as to be made required for sol solution.Illustratively, such as: TEOS (positive silicic acid second
Ester) water that needs of complete hydrolysis and the molar ratio of alkoxide be at least nWater/nAlkoxide=4/1；Need to form metastable sol system
The then molar ratio n of water and alkoxideWater/nAlkoxideIt should be equal to less than 4/1.
After the completion of the suspension and alkoxide sol solution a of material to be packaged are prepared, the two is preferably mixed with the volume ratio of 5:1
Close, obtain mixing suspension, be placed on magnetic stirring apparatus and be stirred continuously, temperature setting be 20~80 DEG C, preferably 40~60
DEG C, revolving speed is 100~300r/m, preferably 170~250r/m.Then, 1~10 hour, preferably 1 is dried under 120 DEG C of degree
~5 hours.The dry powder of acquisition is calcined at 200~500 DEG C, preferably 300~400 DEG C to remove impurity, it is 1~5h of heat preservation, excellent
2~3h is selected, it is air-cooled with furnace later, to obtain the mixed-powder of encapsulating material Yu alkoxide sintering aid a.
It is (0.01~2) according to the mass ratio of sintering aid a and encapsulating material: 100, preferably (0.05 when preparing solution a
~1): 100 ratio is prepared.The concentration of solution a can be 0.01~1M, preferably 0.01M~0.1M, more preferable 0.01M~
0.05M。
In the present invention, the example of encapsulating material includes that garnet and rare earth doped garnet can specifically wrap
Include YAG, LuAG, YGG, GGG, LuGG, YAG:RE, LuAG:RE, YGG:RE, GGG:RE and LuGG:RE, wherein RE be selected from Ce,
Element in Pr, Eu, Nd, Sm, Gd, Yb, Ho, Tm, Dy and Er.
In the present invention, sintering aid a is not particularly limited, and sintering aid commonly used in the art can be used.For example, sintering aid
A can be MgO, SiO2、CaF2、BaF2One or more of.Wherein, the example of the magnesium inorganic salts as MgO precursor includes Mg
(NO3)2·6H2O、MgCl2·6H2O、MgSO4·7H2The water-soluble magnesium salts such as O.The example of magnesium alkoxide as MgO precursor includes
Magnesium ethylate, magnesium isopropoxide, tert-butyl alcohol magnesium etc..As SiO2The example of the alkoxide of precursor include methyl orthosilicate, ethyl orthosilicate,
Positive silicic acid propyl ester, butyl silicate etc..Wherein, ethyl orthosilicate is preferred.
S:2, infiltration-calcining step
Infiltration-calcining step of the invention be will comprising fluorescent powder and be used to encapsulate fluorescent powder encapsulating material and optionally
The green compact of sintering aid a be infiltrated in the precursor solution (hereinafter referred to as " solution b ") of sintering aid b, and will be by infiltration
Green compact are calcined so that the step of precursor of sintering aid b is changed into sintering aid b.
When green compact are impregnated into solution b, liquid level of solution will not have the top of green compact sample.Infiltrating time does not limit especially
Determine, usually 10min~120min, preferably 30min~90min, more preferable 40min~60min.
After the completion of infiltration, green compact are taken out, drying, is then calcined, make mainly to be attached in green compact internal voids
The precursor of sintering aid b is changed into the particle of sintering aid b.
Drying temperature is not particularly limited, and generally can be 50~80 DEG C.Calcination temperature and calcination time are according to different burnings
Tie auxiliary agent and it is different, but usually calcination temperature can be 200~500 DEG C, preferably 300~500 DEG C, more preferable 350~450 DEG C, forge
Burning the time can be 1~5h, preferably 2h~3h.It should be noted that drying can also carry out together with calcining, i.e. selection is suitable
Heating curve is directly calcined.
In the present invention, infiltration-calcine technology can be repeated as many times as desired, and preferably 1~5 time, more preferable 1~3 time.It needs
It is noted that must be all calcined each time so that sintering aid precursor is converted into sintering aid particle.
It is identical with preparing for above-mentioned solution a about the preparation of immersion fluid ie in solution b.The concentration of solution b can be 0.01
~10M, preferably 0.1~10M, more preferable 0.1~1M.
In addition, the content of the sintering aid precursor in solution a and solution b can be equal, it can also be unequal, and two kinds
The concentration of solution can also be identical or different.It is preferred that the concentration of solution b is 5~20 times of solution a, preferably 5~10 times.Because molten
Liquid a is to want relatively low in favor of homogeneous precipitation for being co-precipitated uniformly addition auxiliary agent, concentration；Solution b be for infiltrating,
Concentration can be higher.Know from experience before sintering aid in solution a and fully enter green compact, the sintering aid precursor in solution b only can be small
Part enters green compact, and total sintering aid content in green compact sample can be calculated by this principle.
Taking dry body quality before infiltration sintering aid b solution is m；It takes after infiltration after sintering aid b solution, then after the completion of calcining
Blank quality be M；So the final additive amount of sintering aid b is (M-m)；And the additive amount of sintering aid a is to press
It is had determined before dry body processed, total sintering aid is the summation of sintering aid a and sintering aid b.Meanwhile sintering aid b contains
It measures with 1. infiltrating time, 2. the concentration of compounding agent solution b, the 3. volume of blank and surface area, the porousness 4. inside blank have
It closes；Wherein first three factor can be controlled accurately；It is the pressure applied to powder and powder that 4th factor, which is by blank production,
The factors such as the form of body particle itself determine, can be controlled in a certain range.Therefore, in luminescent ceramic composite
The content of total sintering aid can be more accurately controlled in a certain range.
In addition, sintering aid b is also not particularly limited in the present invention, sintering aid commonly used in the art can be used, for example,
It can be MgO, SiO2、CaF2、BaF2One or more of.Also, sintering aid b can be identical as sintering aid a.
S:3, tableting step
Tabletting will be carried out under larger pressure by infiltration-calcining step green compact.The preferably equal static pressure of tabletting mode；Pressure
Range is 100~300MPa, preferably 180~220MPa.It is appreciated that further by infiltration-calcining step green compact
Tabletting under larger pressure can further decrease the porosity of green compact, improve the densification of luminescent ceramic composite finished product
Degree.Certainly, the mode of tabletting can also be 100~300MPa for dry-pressing formed isobaric sheet mode, pressure limit.It is appreciated that
The step is only to be preferably carried out step, can not include the step in some specific embodiments.
S:4, sintering step
By by the green compact sample of infiltration-calcine technology or tableting step, it is put into sintering furnace, in vacuum or nitrogen/nitrogen hydrogen
It is sintered under gas atmosphere, to obtain luminescent ceramic composite i.e. fluorescent powder-encapsulating material-sintering aid composite material.
Sintering temperature and the sintering time difference according to different encapsulating materials, sintering aid and fluorescent powder, but usually burn
Junction temperature is 1450~1700 DEG C, and preferably 1500~1600 DEG C, sintering time is 1~10h, preferably 2~4h.
In the preparation method of luminescent ceramic composite of the invention, sintering aid is added by the method that liquid phase infiltrates,
The mobility of raw material is improved during normal pressure-sintered or vacuum-sintering, the liquid phase in gap can be more significant, can promote sky
Particle around gap carries out substance transfer, is conducive to eliminate stomata, thus reduces the voidage of final products, improves green compact and burns
Relative density after knot, and improve the optical property of luminescent ceramic composite.
The present invention also provides a kind of luminescent ceramic composites, are made by above-mentioned method of the invention.The present invention
Luminescent ceramic composite be characterized in that comprising fluorescent powder, the encapsulating material for encapsulating the fluorescent powder and sintering
Auxiliary agent.Wherein, the relative density of the luminescent ceramic composite is 94% or more.
Wherein, the particle of encapsulating material is uniformly distributed in around the particle of fluorescent powder, and sintering aid is distributed in encapsulating material
Crystal boundary.
Wherein, in luminescent ceramic composite the total amount of sintering aid be fluorescent powder and encapsulating material gross mass 0.1~
5%, preferably 0.5%~1.5%.Wherein, the total amount of sintering aid is sintering aid a and b quality sum.
Wherein, sintering aid a and b independently are MgO, SiO2、CaF2、BaF2One or more of.
Wherein, encapsulating material YAG, YAG:Ce or Al2O3One or more of.
As shown in figure 3, the content of auxiliary agent increases in gap, the liquid in normal pressure-sintered or vacuum-sintering process void
It meets more significant, the particle around gap can be promoted to carry out substance transfer, be conducive to eliminate stomata, after improving green sintering
Relative density.As a result, the gap of luminescent ceramic composite of the invention is less, relative density is larger, and therefore have
More excellent luminescent properties.
The effect of sintering aid is to generate liquid phase at a lower temperature, and the surface for reducing crystal grain can and increase crystalline substance
The migration rate on boundary provides more crystal boundary channels for the discharge of stomata, it is suppressed that the misgrowth of crystal grain slows down crystal grain
Continuous growth, provides plenty of time for the discharge of stomata.But the additional amount of sintering aid must be strictly controlled, add
Enter amount it is excessive when, the second phase can be formed in ceramics, and influence the transmitance and luminous efficiency of ceramics.
Present invention be described in more detail by the following examples, but the present invention is not limited to following embodiments.
Embodiment 1
The PEG aqueous solution for preparing 1 mass % receives 50 grams of the YAG prepared by coprecipitation as encapsulating material
Rice flour end is mixed with 500 milliliters of PEG aqueous solutions.It will be spare after YAG powder suspension ultrasound 3h.
Weigh 25.64 grams (0.1mol) of Mg (NO3)2·6H2O is configured to the aqueous solution that 1000 milliliters of concentration are 0.1M.
This solution is solution a.
500 milliliters of YAG powder suspensions are mixed with 100 milliliters of solution a, so that MgO and conduct as sintering aid a
The mass ratio of the YAG nano powder of encapsulating material is the ratio of 0.8:100, obtains mixing suspension, is placed in magnetic stirring apparatus
On be stirred continuously, temperature setting be 40 DEG C, revolving speed 170r/m.
Using ammonium hydrogen carbonate as precipitating reagent, it is made into the aqueous solution of about 0.1mol/L, is slowly dropped into the mixing being stirred continuously
Suspension is controlled until by suspension mixed pH value 9 or so.The pH value is kept, continues to stir 2h, to be co-precipitated
Composite granule suspension.
Suspension is centrifugated, washing 3 times is carried out to the powder of acquisition, is then dried in vacuo 5 hours at 100 DEG C.
The dry powder of acquisition is calcined at 300 DEG C to remove impurity, and 2h is kept the temperature, air-cooled with furnace later, obtains YAG-MgO mixing
Powder.
50 grams of YAG-MgO mixed-powder is weighed, two kinds of powder are packed into polytetrafluoroethylene (PTFE) by 50 grams of YAG:Ce fluorescent powder
In ball grinder, suitable ethyl alcohol is added as abrasive solvents, does not use any dispersing agent, with the zirconia ball of ultralow mill mistake rate
Carry out ball milling, Ball-milling Time 30min.
After ball milling ball milling, the dry 1h of vacuum constant temperature crosses 80 mesh, 150 to obtain dry powder later at 120 DEG C of temperature
Mesh, 200 meshes obtain the raw material powder of high fluidity.0.5 gram of raw material powder is weighed to be fitted into punching block, under 100MPa pressure into
Row is pre-stamped, and green compact are obtained after demoulding.
Weigh 25.64 grams (0.1mol) of Mg (NO3)2·6H2O is configured to the aqueous solution that concentration is 0.1M.This solution is
For solution b.
0.5 gram of green compact is infiltrated in 10 milliliters of solution b, so that liquid level of solution did not had the top of green compact sample.When infiltration
Between be 60min, then the green compact after infiltration are taken out, after 80 DEG C of drying, 450 DEG C of calcining is carried out, makes mainly to be attached to green compact
Soluble magnesium nitrate is changed into the magnesia for being insoluble in water in internal voids.
Infiltration technique can be repeated as many times as desired, but must all be calcined each time so that magnesium nitrate converts.This embodiment
It is middle to repeat infiltration-calcine technology 2 times.
By the green compact sample by infiltration technique, it is put into sintering furnace, is burnt under vacuum or nitrogen/nitrogen hydrogen atmosphere
Knot, sintering temperature are 1600 DEG C, soaking time 4h.After the completion of sintering, luminescent ceramic composite YAG:Ce fluorescent powder-is obtained
YAG-MgO。
Embodiment 2
Powder body material in addition to the YAG powder material in embodiment 1 to be changed into YAG:Ce, other technological parameters and scheme are equal
It is in the same manner as in Example 1, to obtain luminescent ceramic composite YAG:Ce fluorescent powder-YAG:Ce-MgO.
Embodiment 3
The TEOS (ethyl orthosilicate) for weighing 2.083 grams (0.01mol) is configured to the ethanol solution that concentration is 0.01M, delays
Slow that ammonium hydroxide is added dropwise, adjusting pH value is about 9.5, by the ageing of 12h, silicon dioxide gel is made, is designated as solution b.
50 grams of YAG phase nanometer powder is weighed, two kinds of powder are packed into polytetrafluoroethylene (PTFE) ball by 50 grams of YAG:Ce fluorescent powder
In grinding jar, add suitable ethyl alcohol as abrasive solvents, do not use any dispersing agent, with it is ultralow mill mistake rate zirconia ball into
Row ball milling, Ball-milling Time 30min.
After ball milling ball milling, dry powder is obtained using vacuum constant temperature is dry, 80 mesh, 150 mesh, 200 meshes is crossed later, obtains
The raw material powder of high fluidity.0.5 gram of raw material powder is weighed to be fitted into punching block, carried out under 100MPa pressure it is pre-stamped, after demoulding
Obtain green compact.
0.5 gram of green compact is impregnated into 10 milliliters of solution b, so that liquid level of solution did not had the top of green compact sample.When infiltration
Between be 90min, then the green compact after infiltration are taken out, after 80 DEG C of drying, 400 DEG C of calcining is carried out, makes mainly to be attached to green compact
Silicon dioxide gel is full of in internal voids.Infiltration technique can be repeated as many times as desired, but must all calcine each time so that
Silicon dioxide gel is converted into silica dioxide granule.The present embodiment repeats infiltration-calcine technology 3 times.
By the green compact sample by infiltration technique, it is put into sintering furnace, is burnt under vacuum or nitrogen/nitrogen hydrogen atmosphere
Knot, sintering temperature are 1500 DEG C, soaking time 6h.After the completion of sintering, luminescent ceramic composite YAG:Ce fluorescent powder-is obtained
YAG-SiO2。
Embodiment 4
Other than changing the YAG powder material in embodiment 3 powder body material of YAG:Ce into, other technological parameters and side
Case is in the same manner as in Example 3, to obtain luminescent ceramic composite YAG:Ce fluorescent powder-YAG:Ce-SiO2。
Embodiment 5
Other than solution b is prepared as described below, other technological parameters and scheme are in the same manner as in Example 1, to obtain
Obtain light ceramic composite material YAG:Ce fluorescent powder-YAG-MgO-SiO2。
The TEOS (ethyl orthosilicate) for weighing 20.833 grams (0.1mol) is configured to the ethanol solution that concentration is 0.1M, delays
The slow deionized water and 0.9gHNO that 11.52g is added dropwise3, adjusting pH value is about 9.5, and by the ageing of 12h, it is molten that silica is made
Glue is designated as solution b.
Embodiment 6
Other than changing the YAG powder material in embodiment 5 powder body material of YAG:Ce into, other technological parameters and side
Case is in the same manner as in Example 5, to obtain luminescent ceramic composite YAG:Ce fluorescent powder-YAG:C-MgO-SiO2。
Embodiment 7
Other than the concentration of solution b in embodiment 1 is become 1M, other technological parameters and scheme are and in embodiment 1
It is identical, to obtain luminescent ceramic composite YAG:Ce fluorescent powder-YAG-MgO.
Embodiment 8
Other than the concentration of solution b in embodiment 1 is become 10M, other technological parameters and scheme are and in embodiment 1
It is identical, to obtain luminescent ceramic composite YAG:Ce fluorescent powder-YAG-MgO.
Comparative example 1
In addition to solution a and solution b is mixed with YAG powder suspension and without infiltration technique other than, with reality
Apply the luminescent ceramic composite as common sample that the identical mode of example 1 prepares comparative example 1.
The physical property and optical property of the luminescent ceramic composite that obtains in embodiment and comparative example is described below
Characterization.
(1) test of density
In the present invention, by using the density of Archimedes's drainage test sample.It is described in detail below.
At about 25 DEG C of temperature, the quality m (g) of sample is first weighed up with the balance that precision is 0.0001；Water will be filled again
Beaker is placed on balance, and balance is zeroed；Sample to be tested is played with filament, sample is submerged in water, keep off beaker
Bottom and wall, obtain balance reading, which is exactly equal to the volume v (ml) of ceramics to be measured；Then it is calculate by the following formula the survey of sample
Metric density: measurement density=m/v (unit g/cm3)。
The relative density of sample=measurement density/theoretical density × 100%
(2) test of optical property
Optical property in the following table 2 uses QY-2000 integrating sphere spectrometer system (being made by Orient KOJI), is swashing
The optical power of blue light-emitting is tested under conditions of being 50mw.
The measurement of common sample obtained in the infiltration sample of green body made from the embodiment of the present invention 1 to 5 and comparative example 1 is close
The result of degree and relative density is shown in Table 1.In embodiment 1 green body obtained infiltration sample with it is obtained general in comparative example 1
The result of the optical property of logical sample is shown in Table 2, and their emission spectrum is shown in Figure 4.
Table 1
Table 2
Shine internal efficiency IE=excitation light power/(total blue light optical power-residue blue light optical power)；
Export the excitation light power (w) of light efficiency EFF=luminous flux (lm)/participation excitation；
The blue light optical power of blue light absorption rate=(total blue light optical power-residue blue light optical power)/total.
As shown in Table 1 it is found that the density and relative density of the green body infiltration sample being prepared by means of the present invention
It is above common sample, thus proves that the content of sintering aid by means of the present invention increases, and therefore improve gained hair
The consistency of light ceramic composite material.
As shown in Table 2 it is found that the green body infiltration luminous internal efficiency of sample being prepared by means of the present invention, EFF,
Blue light absorption rate etc. is above common sample.In addition, as shown in Figure 4, using green body infusion method preparation sample relative to than
Compared with sample prepared by example 1, embodied on emission spectrum, the former spectral emissions intensity is stronger, and peak value is more preferable, in same test
Under system, the luminous efficiency shown is higher.Thus illustrate, luminescent ceramic composite prepared by the method for the present invention
Optical property is improved compared with common sample.
Although the application is described in detail in reference example embodiment, however, it is to be understood that the present invention is not limited to
This.It will be apparent to those skilled in the art that is carried out without departing from the inventive concept of the premise is altered or modified
It all shall be regarded as belonging to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of luminescent ceramic composite, which is characterized in that the described method comprises the following steps:
Green compact comprising fluorescent powder and the encapsulating material and optional sintering aid a that are used to encapsulate the fluorescent powder are infiltrated on
In the precursor solution of sintering aid b, and the green compact by infiltration are calcined so that the precursor of sintering aid b is changed into sintering aid
Infiltration-calcining step of b；
Green compact after calcining are subjected to normal pressure-sintered or vacuum-sintering, to obtain the sintering step of luminescent ceramic composite
Suddenly.
2. the preparation method of luminescent ceramic composite according to claim 1, wherein the total amount of sintering aid is described
The 0.1~5% of fluorescent powder and the encapsulating material gross mass.
3. the preparation method of luminescent ceramic composite according to claim 1 or 2, wherein the precursor of sintering aid b is molten
The concentration of liquid is 0.01~10M.
4. the preparation method of luminescent ceramic composite according to claim 1, wherein infiltrating time be 10min~
120min, and/or, calcination temperature is 200~500 DEG C.
5. the preparation method of luminescent ceramic composite according to claim 1, wherein the infiltration-calcining step carries out
1~5 time.
6. the preparation method of luminescent ceramic composite according to claim 1 further comprises the preparation step of green compact
Suddenly, which includes that comprising the fluorescent powder and will be used to encapsulate the encapsulating material and optional sintering aid of the fluorescent powder
The mixed-powder of a carries out ball milling, drying, sieving, compacting, to obtain green compact.
7. the preparation method of luminescent ceramic composite according to claim 1, wherein sintering aid a and b independently are
MgO、SiO2、CaF2、BaF2One or more of.
8. preparation method according to claim 1, wherein the precursor of sintering aid b is the inorganic salts or alcohol of sintering aid
Salt.
9. a kind of luminescent ceramic composite, it is characterised in that: it includes fluorescent powder, the package material for encapsulating the fluorescent powder
Material and sintering aid, and the relative density of the luminescent ceramic composite is 94% or more.
10. luminescent ceramic composite according to claim 9, it is characterised in that: the particle of the encapsulating material is uniform
It is distributed in around the particle of the fluorescent powder, the sintering aid is distributed in the crystal boundary of the encapsulating material.
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| PCT/CN2017/103432 WO2018233114A1 (en) | 2017-06-20 | 2017-09-26 | Method for preparing luminescent ceramic composite material and luminescent ceramic composite material |
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